CN117042957A - 印刷膜的多层复合物 - Google Patents
印刷膜的多层复合物 Download PDFInfo
- Publication number
- CN117042957A CN117042957A CN202280016123.7A CN202280016123A CN117042957A CN 117042957 A CN117042957 A CN 117042957A CN 202280016123 A CN202280016123 A CN 202280016123A CN 117042957 A CN117042957 A CN 117042957A
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- Prior art keywords
- polyurethane
- multilayer composite
- layer
- polymer layer
- binder
- Prior art date
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/042—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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Abstract
本发明涉及多层复合物,其至少包括第一聚合物层和第二层,所述第一聚合物层含有在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨,所述第二层使用聚氨酯分散体作为粘合剂至少部分与所述第一聚合物层涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的所述侧接合;涉及制造该多层复合物的方法,该方法至少包括以下步骤:(A)提供至少一个在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的第一聚合物层,(B)将作为粘合剂的聚氨酯分散体施加到第一聚合物层上,(C)使来自步骤(B)的第一聚合物层与至少一个第二层接触以获得该多层复合物;涉及该多层复合物用于包装食品或饲料的用途;并涉及包括相应的多层复合物的包装。
Description
本发明涉及至少包括第一聚合物层和第二层的多层复合物,所述第一聚合物层在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂,所述第二层使用聚氨酯分散体作为粘合剂至少部分粘结到该第一聚合物层涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的所述侧上;涉及制造该多层复合物的方法,至少包括以下步骤:(A)提供至少一个在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的第一聚合物层,(B)将作为粘合剂的聚氨酯分散体施加到第一聚合物层上,和(C)使来自步骤(B)的第一聚合物层与至少一个第二层接触以获得该多层复合物;涉及该多层复合物用于包装食品或饲料的用途;并涉及包括相应的多层复合物的包装。
用于包装食品的多层复合物本身是已知的,参见例如“Polyurethanes:Coatings,Adhesives and Sealants”,Meier-Westhues,ISBN 9783866307827,第325至331页。由多层复合物制成的包装通常在它们的外侧上,即在该包装对观察者可见的一侧上,具有印刷在内侧上的透明膜。这也被称为背面印刷或内层印刷。将印刷墨施加到内层上以保护印刷品免受机械损伤。此外,印刷品例如在聚酯膜的内侧上显得光彩照人,由此令包装或包装食品显得品质更高。
除了积极的产品展示方面,内层印刷也是必要的,以便令关于包装的食品、关于成分、关于营养信息或关于包装食品的保质期的信息对零售商和消费者可见。可以通过柔版印刷或凹版印刷方法印刷该膜。用于此的典型膜例如由聚酯、聚丙烯或聚酰胺组成。
用于多层复合物的印刷墨通常是含溶剂的。它们通常不仅含有例如大约70重量%的溶剂,还含有例如大约10重量%的至少一种颜料和例如大约15重量%的至少一种成膜粘结剂。其它成分是助剂和添加剂,例如润湿助剂、脱气剂等,以使印刷墨适配印刷工艺和待印刷的基材。用于溶剂基印刷墨的典型粘结剂包括例如硝化纤维素、聚氯乙烯、聚乙烯醇缩丁醛和聚氨酯。粘结剂的混合物也是可行的。基于聚氨酯的印刷墨可任选在同时使用交联剂异氰酸酯的情况下加工。
如果多层复合物用于包装在包装期间或之后暴露于高温或表现出高温的食品,则使用的印刷墨在这些高工艺温度下也必须是稳定的,即该印刷墨在高温下必须不发生分解或变色。在高温下处理的实例包括例如加热或烹饪该包装中的食品、所谓的袋内泡煮、所谓的食品热填充、所谓的热填充、或填充到多层复合物中之后食品或饲料的蒸汽灭菌——所谓的蒸煮工艺。
除了印刷技术方面和印刷墨中使用的粘结剂的热稳定性之外,市场上的基本期望是仅使用无卤素的印刷墨、胶粘剂、涂料和膜用于包装食品。为此,近年来开发了含有粘结剂聚氨酯的印刷墨。这些印刷墨目前优选用于暴露于高温的多层复合物。
此外,聚氨酯分散体在多层复合物的生产(所谓层压)中用作粘合剂。这些聚氨酯分散体是本领域技术人员已知的。
EP 2 788 447 B1描述了水性聚氨酯分散体用于复合膜层压的用途,其中该聚氨酯的至少10重量%由至少一种非晶态聚酯多元醇构成,并且该聚氨酯分散体含有至少一种外部交联剂。该外部交联剂是具有至少两个异氰酸酯基团的多异氰酸酯。该水性分散体中的聚氨酯优选用氨中和。用于制造该多层复合物的膜材料选自铝箔、印刷的聚酯膜、未印刷的聚酯膜、印刷的聚酰胺膜、未印刷的聚酰胺膜、聚丙烯膜、聚乙烯膜及其组合。公开的复合膜也适于高回弹复合膜,其特别用于蒸煮应用,特别是蒸汽灭菌或巴氏灭菌,以及用于热填充应用。但是,提及的文献没有给出关于在印刷墨中使用的粘结剂的信息。根据该文献使用的胶粘剂的一个缺点是2K(双组分)加工。多异氰酸酯必须在临使用聚氨酯分散体之前添加。以此方式,操作步骤“胶粘剂制造”和“加工”在时间上不能分开。
文献US 6,235,384 B1公开了包括两个用可固化胶粘剂粘结的柔性膜的层压体。该胶粘剂通过在临使用前混合两种组分来形成,其中一种组分是至少一种具有至少一个羧酸或磺酸基团的聚氨酯。该羧酸或磺酸基团用氨来中和。第二组分是用于聚氨酯聚合物的交联剂。其含有大量碳二亚胺、氮丙啶或环氧基团。所述层压体还可用于热填充或袋内泡煮工艺。所述文献未提及印刷膜。该工艺的一个缺点同样是需要双组分加工。
向聚氨酯分散体中添加交联剂与层压工艺解耦,即避免双组分程序,在经济上是有利的,因为例如在中断层压工艺的情况下,这使得胶粘剂从层压设备的胶粘剂储器中再次取出并在稍晚的时间点再次使用。在根据现有技术的双组分加工的情况下,高达20重量%的胶粘剂可能在高速层压设备上的工业制造过程中变成废料。这种废料在经济和生态上都是成问题的。
因此,本发明的目的是提供多层复合物,特别用于食品的包装的多层复合物,其中该多层复合物应印刷有基于聚氨酯的印刷墨,并特别应当适于包装食品或饲料,特别是在袋内泡煮、热填充和蒸煮应用中。用于该膜层压的胶粘剂还应当是无卤素的,并且能1K(单组分)加工。
根据本发明,通过一种多层复合物来实现这些目的,所述多层复合物至少包括第一聚合物层和第二层,所述第一聚合物层在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨,所述第二层使用聚氨酯分散体作为粘合剂至少部分粘结到该第一聚合物层涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的所述侧上。
根据本发明的多层复合物包括至少一个在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的第一聚合物层。
根据本发明,该多层复合物除了第一聚合物层之外还可以包括其它层,所述其它层至少部分但优选在其整面地粘结到第一聚合物层和/或存在的其它层上。根据本发明,除第一聚合物层外,该多层复合物含有1至6个其它层。
第一聚合物通常可含有本领域技术人员认为合适的任何材料,优选由所述材料组成。在根据本发明的多层复合物中,所述至少一个第一聚合物层的材料优选选自聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)、聚酯、聚乙酸酯、赛璐酚、聚乳酸(PLA)及其混合物。根据本发明,该第一聚合物层特别优选由聚对苯二甲酸乙二醇酯,聚丙烯或聚酰胺组成;更优选地,该第一聚合物层是聚对苯二甲酸乙二醇酯膜、聚丙烯膜或聚酰胺膜。
如果根据本发明聚乙烯膜或聚丙烯膜用作第一聚合物层,其通常含有润滑剂,例如油酸酰胺和/或芥酸酰胺。其优点在于避免了层压工艺过程中或进一步加工成包装的过程中在高带速下该膜的撕裂或拉伸。
根据本发明存在的第一聚合物层通常具有5至200μm、优选12至60μm的厚度。
任选的其它存在的层同样可以含有聚合物材料或由聚合物材料组成。适于任选存在的其它层的聚合物材料选自聚合物材料,特别是膜的形式,选自聚乙烯(PE)(特别是LDPE、LLDPE、HDPE)、聚丙烯(PP),特别为未拉伸膜(cPP)、单侧拉伸膜(oPP)或双侧拉伸膜(BOPP)形式,选自聚酰胺(PA)、聚酯,特别是聚对苯二甲酸乙二醇酯(PET)、聚乙酸酯、赛璐酚、聚乳酸(PLA)及其混合物。根据本发明,该任选存在的其它层特别优选由聚对苯二甲酸乙二醇酯、聚丙烯或聚酰胺组成;更优选该任选存在的其它层是聚对苯二甲酸乙二醇酯、聚丙烯或聚酰胺膜。该任选存在的其它层可任选配有如上所述的润滑剂。该任选存在的其它层也可由其它非聚合物材料形成,例如金属,特别是铝,或纸张,或其组合。
如果本发明任选存在的其它层含有聚合物材料或由聚合物材料组成,则其通常具有5至200μm、优选12至60μm的厚度。如果根据本发明任选存在的其它层含有金属,特别是铝或由金属,特别是铝组成,则其通常具有5至100μm、优选9至15μm的厚度。由纸组成的任选存在的层通常具有5至200μm、优选10至50μm的厚度。
根据本发明,第一聚合物层和/或任选存在的其它层的尺寸不受限制,而是取决于根据本发明的多层复合物的用途,例如作为食品或饲料的包装。本发明不仅涉及作为卷材的根据本发明的多层复合物,例如在用根据本发明的多层复合物包装食品或饲料之前,特别是作为具有本领域技术人员已知尺寸的原材料,还涉及同样具有本领域技术人员已知尺寸的食品或饲料的实际包装。
该任选存在的其它层可以是透明的或不透明的,即例如用已知染料染色。此外,该任选存在的其它层可以是印刷或未印刷的。
该第一聚合物层根据本发明在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨。
在本发明的上下文中,第一聚合物层优选在至少一侧上,可能还在两侧上印刷有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨。根据本发明,该印刷品可以完全或部分、优选部分覆盖该第一聚合物层的印刷侧。
含有至少一种聚氨酯作为粘结剂的印刷墨本身是本领域技术人员已知的,并例如描述在DE 60301623 T2、DE 60302141 T2或DE 60100208 T2中。
适于作为粘结剂的聚氨酯特别可以通过使过量的一种或多种脂族二异氰酸酯与一组由一种或多种各自具有不超过2000g/mol的平均分子量的聚醚多元醇与至少一种二胺组成的异氰酸酯反应性组分反应以获得预聚物和相对于预聚物的游离NO基团过量的异佛尔酮二胺与选自乙二胺、1,2-二氨基环己烷和2,2,4-或2,4,4-三甲基二氨基己烷(TMDA)的第二二胺的混合物来获得。
脂族二异氰酸酯的实例是直链脂族、支链脂族或脂环族二异氰酸酯。该二异氰酸酯优选包含1至10个碳原子。优选的二异氰酸酯的实例是1,4-二异氰酸根合丁烷、1,6-二异氰酸根合己烷、1,5-二异氰酸根合-2,2-二甲基戊烷、4-三甲基-1,6-二异氰酸根合己烷、1,10-二异氰酸根合癸烷、1,3-和1,4-二异氰酸根合环己烷、1-异氰酸根合-5-异氰酸根合甲基-3,3,5-三甲基环己烷(异佛尔酮二异氰酸酯(IPDI))、2,3-、2,4-和2,6-二异氰酸根合-1-甲基环己烷、4,4’-和2,4’-二异氰酸根合二环己基甲烷、1-异氰酸根合-3-(4)-异氰酸根合甲基-1-甲基环己烷、4,4’-和2,4’-二异氰酸根合二苯基甲烷及其混合物或2,2,4-或2,4,4-三甲基二异氰酸根合己烷(TMDI)。
优选可用的该聚氨酯的聚醚多元醇组分例如符合下式:
HO-[-RO-]n-H,
其中R是直链或支链C2至C10烃基团。R优选是包含2至4个碳原子的亚烷基。
优选的聚醚多元醇的实例包括聚乙二醇醚(PEG)、聚丙二醇醚(PPG)和聚四亚甲基醚二醇(聚THF)或其混合物。特别优选使用聚THF。在上式中,选择n以使聚醚多元醇的平均分子量不超过2000g/mol、优选小于1500g/mol和特别优选1000g/mol或更低。本发明的特别优选的聚醚多元醇是聚THF 1000。
作为其它异氰酸酯反应性组分,加入至少一种二胺。该二胺可以是具有伯氨基或仲氨基的任何脂族、脂环族、芳族或杂环二胺。实例包括乙二胺、1,2-二氨基丙烷、1,3-二氨基丙烷、二氨基丁烷、六亚甲基二胺、1,4-二氨基环己烷、3-氨基甲基-3,5,5-三甲基环己胺(异佛尔酮二胺)、间苯二甲胺或1,3-双(氨基甲基)环己烷。特别优选异佛尔酮二胺。
作为其它异氰酸酯反应性成分可以加入一种或多种平均分子量等于或小于800g/mol的多元醇,例如1,4-丁二醇、1,6-己二醇、新戊二醇、二羟基聚醚多元醇、聚酯多元醇等。
该一种或多种二异氰酸酯与异氰酸酯反应性组分彼此反应以形成第一异氰酸酯封端的预聚物。二异氰酸酯组分对异氰酸酯反应性组分的当量比优选为3.6:1至1.1:1、优选2:1至1.1:1。
异氰酸酯反应性组分可以平行或顺序加入到(一种或多种)异氰酸酯中。在顺序添加异氰酸酯反应性成分的情况下,优选初始加入聚醚多元醇成分,接着加入(一种或多种)二胺成分,并可选地接着加入至少一种多元醇。该反应在本领域技术人员公知的条件下进行。该反应可以在溶剂的存在下使用已知催化剂来进行。
合适的溶剂的实例包括乙酸烷基酯,例如乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯和乙酸戊酯。溶剂的总量通常为反应混合物的0重量%至90重量%、优选反应混合物的25重量%至60重量%。
催化剂可用于加速二异氰酸酯与二醇的反应。合适的催化剂是锡衍生物,例如辛酸锡、草酸锡、二月桂酸二丁基锡,锌衍生物如二乙酸锌、双乙酰丙酮锌,或有机钛化合物如钛酸四丁酯,或其混合物。
可以存在其它添加剂或添加料。例如可以加入抗氧化剂如Irganox1076(十八烷基-3,5-二叔丁基-4-羟基氢化肉桂酸酯)。
异氰酸酯封端的预聚物的形成通常在0℃至130℃、优选50℃至90℃的温度下进行。反应时间例如为1至12小时、优选1至4小时。
如此形成的异氰酸酯封端的预聚物优选用异佛尔酮二胺(IPDA)和选自乙二胺(EDA)、1,2-二氨基环己烷和2,2,4-或2,4,4-三甲基二氨基己烷(TMDA)的第二二胺的混合物扩链。第二二胺对IPDA的比率优选为10:1至2:1,特别是5:1至3:1。异氰酸酯封端的预聚物对二胺组分的混合物的当量比率例如为1:5至1:1.1、优选1:4至1:1.1。
该聚氨酯可以在溶剂如醇,优选乙醇,或酯如乙酸正丙酯中稀释以获得清澈的溶液。
该聚氨酯优选具有20000至80000g/mol、优选25000至55000g/mol的平均分子量。该聚氨酯具有例如20%至30%的氨基甲酸酯化程度。
所用的印刷墨可适配于不同类型的塑料基材和/或涂施工艺的需要。
除了至少一种聚氨酯外,所用印刷墨包含通常用于特定印刷工艺的成分,特别是雕刻印刷工艺、柔版印刷工艺或凹版印刷工艺。除了至少一种聚氨酯外的主要成分是至少一种颜料和/或至少一种染料,至少一种溶剂和任选的附加添加剂。
在所用印刷墨中,树脂,例如硝化纤维素可用作染料或颜料的载体。作为溶剂可以使用通常使用的溶剂,如醇,特别是乙醇或异丙醇。
添加剂为例如表面活性物质/表面活性剂、增塑剂、稳定剂或蜡。
根据本发明,一种或多种含有至少一种聚氨酯作为粘结剂的印刷墨可以施加到第一聚合物层上。除了所述至少一种含有至少一种聚氨酯作为粘结剂的印刷墨外,还可以存在至少一种含有不同于聚氨酯的粘结剂的印刷墨。
用于将所述至少一种印刷墨施加到第一聚合物层上的方法是本领域技术人员已知的,例如雕刻印刷工艺、柔版印刷工艺或凹版印刷工艺。
根据本发明的多层复合物包含至少一个第二层,所述第二层使用聚氨酯分散体作为粘合剂至少部分粘结到该第一聚合物层涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的所述侧上。
根据本发明存在的第二层同样可以含有聚合物材料或由聚合物材料组成。适于第二层的聚合物材料选自聚合物材料,特别是膜的形式,选自聚乙烯(PE)(特别是LDPE、LLDPE、HDPE)、聚丙烯(PP),特别为未拉伸膜(cPP)、单侧拉伸膜(oPP)或双侧拉伸膜(BOPP)形式,选自聚酰胺(PA)、聚酯,特别是聚对苯二甲酸乙二醇酯(PET)、聚乙酸酯、赛璐酚、聚乳酸(PLA)及其混合物。根据本发明,该第二层特别优选由聚对苯二甲酸乙二醇酯、聚丙烯或聚酰胺组成;更优选该第二层是聚对苯二甲酸乙二醇酯膜、聚丙烯膜或聚酰胺膜。该第二层可任选配有如上所述的润滑剂。
该第二层可优选由非聚合物材料形成,例如金属,特别是铝,或纸张或其组合。本发明优选涉及根据本发明的多层复合物,其中至少一个其它层是聚合物层或由至少一种金属、优选铝组成的层。
根据本发明,特别优选的是该多层复合物的第二层由金属、特别是铝组成。
如果第二层由聚合物材料组成或含有聚合物材料,该第二层通常具有5至200μm、优选12至60μm的厚度。由纸张组成的第二层通常具有5至200μm、优选10至50μm的厚度。
在其中根据本发明的第二层由金属(特别是铝)组成或含有金属(特别是铝)的优选情况下,其通常具有5至100μm、优选9至15μm的厚度。
根据本发明,关于第二层的宽度和长度的尺寸不受限制,但优选取决于第一聚合物层和任选存在的其它层的尺寸。该第二层因此优选具有与第一聚合物层和根据本发明的整个多层复合物相同的尺寸。
该第二层可以是透明的或不透明的,即例如用已知染料染色。此外,该第二层可以是印刷或未印刷的。由于第二层优选由金属组成、更优选由铝组成,其优选是不透明的。
本发明优选涉及根据本发明的多层复合物,其中该第一聚合物层由聚酯组成,且该第二层由铝组成。
存在于根据本发明的多层复合物中的层,特别是第一聚合物层、任选存在的其它层和第二层,任选用至少含有聚氨酯的印刷墨印刷或用铝或二氧化硅蒸镀,根据本发明可以以任何可能方式、特别是顺序来彼此组合。多层复合物的构造例如取决于阻隔效果与成本方面的要求。
根据本发明,优选的是根据本发明的多层复合物包括第一聚合物层和第二层,所述第一聚合物层在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨,所述第二层使用聚氨酯分散体作为粘合剂至少部分粘结到该第一聚合物层涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的所述侧上。
根据本发明,优选的是根据本发明的多层复合物包括第一聚合物层和特别由金属组成、优选由铝组成的第二层和第三聚合物层,所述第一聚合物层在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂印刷墨,所述第二层使用聚氨酯分散体作为粘合剂至少部分粘结到该第一聚合物层涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的所述侧上,所述第三聚合物层优选使用粘合剂、特别是聚氨酯分散体至少部分粘结到该第二层未与第一聚合物层粘结的侧上。
如果根据本发明的多层复合物包含具有低能表面(即表面能<38mN/m的表面)的层,根据本发明优选的是对这些施以用常压等离子体(电晕)的预处理。对第一聚合物层而言可以在临施加作为粘合剂的聚氨酯分散体之前进行此类预处理,或者对第二层而言在引入层压机之前进行此类预处理。
根据本发明的多层复合物的至少两个层用聚氨酯分散体作为粘合剂粘结。根据本发明优选的是所用粘合剂是至少一种1K(单组分)聚氨酯分散体。根据本发明,这应理解为是指作为粘合剂使用在施加到至少一个聚合物层之前不必与其它组分交联的分散体。
根据本发明,优选的是所用粘合剂是至少一种聚氨酯分散体,其是至少一种水性聚氨酯分散体(I)和至少一种亲水化多碳二亚胺的至少一种水性分散体(II)的混合物。
在本发明的上下文中,水性聚氨酯分散体(I)是聚氨酯-聚脲聚合物在水中的分散体。在本发明的上下文中,术语“聚氨酯”涉及具有聚氨酯和/或聚脲基团的聚合化合物。
作为构造组分,根据本发明优选使用的聚氨酯含有以下组分:
(A)至少一种分子量为至少500g/mol的非晶态聚酯多元醇,
(B)至少一种二异氰酸酯和/或多异氰酸酯组分,
(C)至少一种选自一元至三元醇的化合物,其附加地含有至少一个离子基团或至少一个可转化为离子基团的基团,
(D)至少一种选自中和胺和氨的化合物,
(E)至少一种作为扩链剂的二胺,和
(F)任选的其它异氰酸酯反应性化合物。
在本发明的上下文中,非晶态是其组成单元没有排列在晶格中,即非结晶的固体。根据本发明,非晶态聚酯特别是在根据DIN 65467-1999-03的DSC测量中在20K/分钟的加热速率下在-30℃至+100℃的温度范围内未显示熔融峰的聚酯。
该聚氨酯聚合物优选含有至少一种非晶态聚酯多元醇、优选聚酯二醇,其量为至少20重量%、优选至少40重量%、特别优选至少60重量%,在每种情况下基于该聚氨酯聚合物计。该聚氨酯聚合物中至少一种非晶态聚酯多元醇的量的上限优选为至多90重量%,例如至多88重量%,但也可以超过90重量%。
该至少一种非晶态聚酯多元醇(优选聚酯二醇)优选具有至少500g/mol的平均分子量。该平均分子量特别优选为1000至4000g/mol、特别优选1700至2500g/mol,在每种情况下通过凝胶渗透色谱法(GPC)根据DIN 55672-1:2016-03在四氢呋喃中在23℃下相对于聚苯乙烯标样来测定。
根据本发明使用的至少一种非晶态聚酯多元醇优选是至少一种非晶态聚酯二醇。优选使用至少一种芳族二羧酸来制造该至少一种非晶态聚酯二醇(A)。间苯二甲酸和对苯二甲酸是优选的。间苯二甲酸是特别优选的。
在一个优选实施方案中,至少一种非晶态聚酯二醇(A)的制造使用由至少一种具有3至10、优选4至8个碳原子的脂族二羧酸和至少一种芳族二羧酸组成的羧酸混合物。该混合比优选为0.5:1至2:1。优选的二羧酸混合物是己二酸/间苯二甲酸,特别为0.5:1至2:1的比。
为了制造至少一种非晶态聚酯二醇(A),作为多元醇可以使用例如乙二醇、丙烷-1,2-二醇、丙烷-1,3-二醇、丁烷-1,3-二醇、丁烯-1,4-二醇、丁炔-1,4-二醇、戊烷-1,5-二醇、新戊二醇、双(羟甲基)环己烷如1,4-双(羟甲基)环己烷、2-甲基丙烷-1,3-二醇、甲基戊二醇、还有二乙二醇、三乙二醇、四乙二醇、聚乙二醇、二丙二醇、聚丙二醇、二丁二醇和聚丁二醇。优选通式HO-(CH2)x-OH的醇,其中x是1至20的整数、优选2至20的偶数。其优选实例是乙二醇、丁烷-1,4-二醇、己烷-1,6-二醇、辛烷-1,8-二醇和十二烷-1,12-二醇。新戊二醇也是优选的。丁烷-1,4-二醇、己烷-1,6-二醇和新戊二醇是特别优选的。
二异氰酸酯(B)特别包括通式X(NCO)2的二异氰酸酯,其中X是具有4至15个碳原子的脂族烃基团、具有6至15个碳原子的脂环族或芳族烃基团或具有7至15个碳原子的脂族烃基团。此类二异氰酸酯的实例是四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、1,4-二异氰酸根合环己烷、1-异氰酸根合-3,5,5-三甲基-5-异氰酸根合甲基环己烷(IPDI)、2,2-双(4-异氰酸根合环己基)丙烷、三甲基己烷二异氰酸酯、1,4-二异氰酸根合苯、2,4-二异氰酸根合甲苯、2,6-二异氰酸根合甲苯、4,4’-二异氰酸根合二苯基甲烷、2,4'-二异氰酸根合二苯基甲烷、对二甲苯二异氰酸酯、四甲基二甲苯二异氰酸酯(TMXDI)、双(4-异氰酸根合环己基)甲烷(HMDI)的异构体如反式/反式、顺式/顺式和顺式/反式异构体,以及由这些化合物组成的混合物。此类二异氰酸酯是市售可得的。
根据本发明,优选六亚甲基二异氰酸酯、四甲基二甲苯二异氰酸酯(TMXDI)和1-异氰酸根合-3,5,5-三甲基-5-异氰酸根合甲基环己烷(IPDI),特别优选1-异氰酸根合-3,5,5-三甲基-5-异氰酸根合甲基环己烷(IPDI)。
显然还可共同使用部分的聚氨酯化学中本身已知的更高官能度的多异氰酸酯,或本身已知并例如包含碳二亚胺、脲基甲酸酯、异氰脲酸酯、氨基甲酸酯和/或缩二脲基团的改性多异氰酸酯作为组分(B)。
优选以少量共同使用的包含异氰脲酸酯和/或缩二脲基团的多异氰酸酯。市售化合物例如是六亚甲基二异氰酸酯的异氰脲酸酯或缩二脲。
附加地含有至少一个离子基团或至少一个可转化为离子基团的基团的合适的组分(C)例如是一元至三元醇、单氨基羧酸和/或二氨基羧酸。
该一元至三元醇(C)特别含有离子基团如磺酸根、羧酸根和磷酸根基团。
术语离子基团还应涵盖可转化为离子基团的基团。相应地,可通过中和转化成离子基团的羧酸、磺酸或磷酸基团也被认为是离子基团。二羟基羧酸和二氨基羧酸优选作为化合物(C)。二羟基羧酸,特别是二羟甲基丙酸(DMPS)和二羟甲基丁酸(DMBS)是非常特别优选的。
氨和叔胺例如适于作为组分(D)。特别合适和优选的叔胺是三乙胺、二甲基环己胺和乙基二异丙胺。
还可以使用其它胺来形成盐,例如二乙醇胺、三乙醇胺、二甲基乙醇胺、甲基二乙醇胺、氨基甲基丙醇以及所述胺和其它胺的混合物。
氨和三乙胺特别优选作为(D)。氨是非常特别优选的。一部分氨初始通过加成和链终止与由组分(A)、(B)和(C)组成的预聚物中存在的NCO基团反应,剩余部分作为中和胺反应。当使用氨时,可以通过预聚物与作为扩链剂(E)的二胺的预先反应来改变剩余NCO基团的数目,并由此改变扩链与链终止之间的比率。这使得可以调节聚合物的分子量。当使用氨时,预聚物有利地初始与组分(E)反应,然后才加入氨作为组分(D)。
二胺(E)的实例是1,2-乙二胺(乙二胺)、1,6-六亚甲基二胺、1-氨基-3,3,5-三甲基-5-氨基甲基环己烷(异佛尔酮二胺)、哌嗪、1,4-二氨基环己烷和双(4-氨基环己基)甲烷。己二酸二酰肼、肼和水合肼也是合适的。显然,也可以使用多种提及的、任选还一起使用未提及的化合物(D)的混合物。
优选的组分(E)是乙二胺和异佛尔酮二胺。乙二胺是非常特别优选的。
在本发明的一个非常特别优选的实施方案中,氨用作组分(D),且乙二胺用作组分(E)。
合适的其它异氰酸酯反应性化合物(F)原则上包括不同于(A)至(E)的所有化合物,其不同于异氰酸酯反应性化合物,例如分子量为62至499g/mol的二醇、结晶聚酯二醇、聚合物二醇如聚醚、内酯或聚碳酸酯、一元醇、一元胺和多胺。
根据本发明使用的水性聚氨酯分散体的制造可以采用现有技术中已知的任何方法,例如乳化剂-剪切力、丙酮、预聚物混合、熔体乳化、酮亚胺和固态自发分散法或其衍生方法。这些方法的概述可以在Methoden der organischen Chemie[有机化学方法]Houben-Weyl,Erweiterungs-undzur 4.Auflage[扩展与补充卷,第4版],第E20卷,H.Bartl和J.Falbe,Stuttgart,New York,Thieme 1987,第1671至1682页中找到。优选熔体乳化、预聚物混合和丙酮法。特别优选丙酮法。丙酮法的使用和实施是现有技术,并且是本领域技术人员例如由EP 0 232 778已知的。
根据本发明使用的聚氨酯分散体具有35重量%至48重量%、优选38重量%至45重量%的固含量。
亲水化多碳二亚胺(II)的水性分散体在本发明的上下文中是包含碳二亚胺基团的交联剂,其分散、乳化、溶解在水中或可分散、可乳化和/或可溶解在水中。
根据本发明,优选含有碳二亚胺结构的交联剂,其每分子平均含有3至20个、特别优选4至8个碳二亚胺结构单元。
此类碳二亚胺交联剂例如可以通过二异氰酸酯的碳二亚胺化来获得,所述二异氰酸酯例如四亚甲基二异氰酸酯、甲基五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、1,4-二异氰酸根合环己烷、1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷、4,4’-二异氰酸根合二环己基甲烷、4,4’-二异氰酸根合二环己基丙烷-(2,2)、1,4-二异氰酸根合苯、2,4-二异氰酸根合甲苯、2,6-二异氰酸根合甲苯、4,4'-二异氰酸根合二苯基甲烷、2,2’-和2,4’-二异氰酸根合二苯基甲烷、四甲基二甲苯二异氰酸酯、对二甲苯二异氰酸酯、对异亚丙基二异氰酸酯,任选同时使用单官能异氰酸酯如硬脂基异氰酸酯、苯基异氰酸酯、丁基异氰酸酯、己基异氰酸酯和/或更高官能度的异氰酸酯如三聚体、脲二酮、脲基甲酸酯、提及的示例性二异氰酸酯的缩二脲,和随后、同时或甚至在先的与亲水化组分的反应,所述亲水化组分例如由醇或胺开始的基于环氧乙烷聚合物或环氧乙烷/环氧丙烷共聚物的单官能或双官能聚醚。
优选的碳二亚胺通过1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷和/或4,4'-二异氰酸根合二环己基甲烷的碳二亚胺化来获得。
同样可以使用包含例如基于不同异氰酸酯的碳二亚胺的混合碳二亚胺。
合适的碳二亚胺的实例例如是均来自日本东京Nisshinbo Industries的SV-02、/>V-02-L2、/>E-02,和来自CovestroDeutschland AG的/>XP 2802。优选的碳二亚胺是/>V-02-L2和Desmodur/>2802,Desmodur/>是特别优选的。
合适的碳二亚胺同样包括水性碳二亚胺分散体或碳二亚胺乳液或碳二亚胺溶液和/或水分散性碳二亚胺,其含有以下物质的反应产物:
a)至少一种碳二亚胺,其具有平均3至20个、优选4至8个基于双官能异氰酸酯的碳二亚胺结构单元,特别是W、/>I、/>H和/或T(均来自Bayer MaterialScience,德国),和
b)亲水性组分,例如至少一种基于环氧乙烷或基于环氧乙烷与环氧丙烷的羟基官能聚醚,例如甲氧基聚乙二醇、乙氧基聚乙二醇、丁氧基聚乙二醇,各自具有350至3000g/mol的分子量,如MPEG 750、MPEG 550、MPEG 350,均来自DOW ChemicalCompany,USA;Polyether LB 25,来自Bayer MaterialScience,德国和/或相应的氨基官能聚醚和/或起离子亲水化作用的物质,如氨基羧酸、羟基羧酸或氨基磺酸的盐,例如二羟甲基丙酸、二羟甲基丁酸、羟基新戊酸、氨基乙磺酸的盐,
c)任选其它羟基和/或氨基官能和/或其他异氰酸酯反应性化合物,例如一元醇,如乙二醇单丁醚、二乙二醇丁基醚、乙氧基二甘醇、甲氧基丙醇、甲氧基乙二醇、甲醇、苄醇、脂肪醇、2-乙基己醇、硬脂醇、油醇、乙醇、丁醇、异丙醇、己醇、环己醇、辛醇、戊醇和/或单胺、肟、内酰胺如二乙胺、二异丙胺、三唑、二甲基三唑、二甲基吡唑、吗啉、丁酮肟、己内酰胺、叔丁基苄胺和/或丙二酸二烷基酯、乙酰乙酸酯、环戊酮羧烷基酯和/或二醇、二胺、氨基醇、三醇如三羟甲基丙烷、甘油、新戊二醇、丁二醇、乙二醇、环己二醇、环己烷二甲醇、丙二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇、乙醇胺、二乙醇胺、异丙醇胺、二异丙醇胺、三乙醇胺、羟乙基乙二胺、乙二胺、异佛尔酮二胺、六亚甲基二胺、肼。
组分a)、b)和c)可以以任何顺序反应,任选还在溶剂的存在下。
碳二亚胺ii)优选是50重量%至97重量%的组分a)、3重量%至40重量%的组分b)和0重量%至25重量%的组分c)的反应产物,其中组分a)、b)和c)的总和在每种情况下为100重量%。
该碳二亚胺特别优选是60重量%至90重量%的组分a)、5重量%至27重量%的组分b)和0.5重量%至15重量%的组分c)的反应产物,其中组分a)、b)和c)的总和在每种情况下为100重量%。
该碳二亚胺可以通过已知方法来制造。合适的催化剂为例如杂环含磷化合物、金属羰基化合物、环磷烯(Phospholine)、磷杂环戊烯(Phospholene)和磷啶(Phospholidine)以及其氧化物和硫化物。
优选的是碳二亚胺初始通过在合适的催化剂(例如磷杂环戊烯氧化物)的存在下将至少一种至少双官能的二异氰酸酯加热到100℃至250℃来反应以消除二氧化碳,直到实现所需转化率,该碳二亚胺随后在进一步的反应步骤中与组分b)反应并任选同时或随后与组分c)反应,并任选随后分散、乳化或溶解。
根据本发明使用的亲水化聚碳二亚胺的水性分散体具有例如37重量%至42重量%的固含量。
根据本发明用作粘合剂的水性聚氨酯分散体优选含有70重量%至99重量%的根据本发明的聚氨酯分散体(I)和1重量%至30重量%的亲水化多碳二亚胺(II)的水性分散体。特别优选用作粘合剂的聚氨酯分散体含有80重量%至97重量%的根据本发明的聚氨酯分散体(I)和3重量%至20重量%的亲水化多碳二亚胺(II)的水性分散体。非常特别优选用作粘合剂的聚氨酯分散体含有85重量%至92重量%的根据本发明的聚氨酯分散体(I)和8重量%至15重量%的亲水化多碳二亚胺(II)的水性分散体。
用作粘合剂的水性聚氨酯分散体可以通过简单混合组分(I)和(II)来制造。初始装入水性聚氨酯分散体(I),并在搅拌下加入亲水化多碳二亚胺(II)的水性分散体。该粘合剂分散体至少在数小时内是储存稳定的,并因此适于单组分加工。
根据本发明用作粘合剂的水性聚脲分散体可以单独使用或与涂料和胶粘剂技术中已知的粘结剂、助剂和添加剂物质一起使用,特别是乳化剂和光保护剂如UV吸收剂和空间位阻胺(HALS)、还有抗氧化剂、填料和助剂,例如抗沉降剂、消泡剂和/或润湿剂、流动控制剂、反应性稀释剂、增塑剂、催化剂、辅助溶剂和/或增稠剂和添加剂,例如颜料、染料或消光剂。还可以加入增粘剂,也即所谓的增稠剂。
该添加剂可以在临加工前添加到根据本发明使用的粘合剂中。但是,还可在分散聚氨酯之前或期间添加至少一部分该添加剂。
可以添加到单个组分和/或整个混合物中的这些物质的选择与计量添加原则上是本领域技术人员已知的,并可以通过简单的初步试验在无需过度努力的情况下确定并对特定应用来调整。
本发明进一步涉及制造根据本发明的多层复合物的方法,至少包括以下步骤:
(A)提供至少一个在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的第一聚合物层,
(B)将作为粘合剂的聚氨酯分散体施加到第一聚合物层上,
(C)使来自步骤(B)的第一聚合物层与至少一个第二层接触以获得根据本发明的多层复合物。
下面详细描述本发明的方法的各个步骤。
根据本发明的多层复合物的制造尤其以半连续干层压工艺来实现。
步骤(A)包括提供至少一个第一聚合物层,其在至少一侧上至少部分或完全涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨。
根据本发明,在步骤(A)中可以仅提供一个第一聚合物层。还可在步骤(A)中提供第一聚合物层与其它层的组合。
该第一聚合物层在至少一侧上至少部分或完全涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨。
用相应的印刷墨涂覆的方法本身是本领域技术人员已知的,例如雕刻印刷工艺、柔版印刷工艺或凹版印刷工艺。第一聚合物层的涂层可以是单色或多色的,可以仅部分覆盖该层或完全覆盖该层。
根据本发明的方法的步骤(A)中的提供例如通过使来自放卷工位的第一聚合物层穿过涂施机。
根据本发明的方法的步骤(B)包括将作为粘合剂的聚氨酯分散体施加到第一聚合物层上。
步骤(B)通常可以以本领域技术人员已知的所有方式来进行,例如步骤(B)可以包括使用凹印辊或光辊将粘合剂施加到第一聚合物层上。在此辊旋转可以在第一聚合物层的运动方向上或在相反方向上。在辊涂施后,可以例如用旋转的平滑杆处理粘合剂层,这通常获得更光滑的粘合剂层。尤其在部分透明多层复合物的情况下,这使得可以改善粘合剂层的外观。
其它适于步骤(B)中施加聚氨酯分散体的技术是喷涂、借助油漆喷雾器涂施或幕涂。
在步骤(B)中,调节聚氨酯分散体的涂施速率,以使得在干燥后,即在蒸发水之后,在第一聚合物膜上存在0.1至20g/m2、优选0.5至7g/m2的聚氨酯聚合物。
在施加聚氨酯分散体之后,优选干燥涂覆的第一聚合物层,特别是穿过隧道式干燥器。在隧道式干燥器中,聚氨酯分散体层被干燥,并且所有在干燥条件下挥发的成分被蒸发。隧道式干燥器中的温度例如为50℃至200℃、优选70℃至90℃。
干燥步骤中的带速度例如取决于分散体的涂施速率、分散体中的聚合物比例、隧道式干燥器的长度、隧道式干燥器中的温度、隧道式干燥器中的空气流、隧道式干燥器中的进料空气量以及进料空气的大气湿度。带速度对工艺的经济性是决定性的,并优选为100至1000m/min、优选150至300m/min。
根据本发明的方法的步骤(C)包括使来自步骤(B)的第一聚合物层与至少一个第二层接触以获得根据本发明的多层复合物。
根据本发明的方法的步骤(C)优选通过在可加热层压机中将从隧道式干燥器中离开后来自步骤(B)的包含干燥的聚氨酯聚合物的第一聚合物层与第二层层压,其中辊对优选由钢辊和橡胶辊组成。该第二层是进料层。
步骤(C)中的压力,特别是层压装置中的辊之间的压力在此优选为100至3000KN/m2、优选500至2000kN/m2。步骤(C)中的温度,特别是层压机中钢辊的温度为20℃至200℃、优选40℃至90℃。
在步骤(C)之后,将获得的根据本发明的多层复合物卷绕并储存直到进一步加工,即直到包装食品或饲料。
本发明进一步涉及根据本发明的多层复合物用于包装食品或饲料的用途、特别是用于在高温(例如90℃至140℃)下处理例如最多60分钟。实例包括加热或烹饪该包装中的食品、所谓的袋内泡煮、所谓的食品热填充、所谓的热填充、或填充到多层复合物中之后食品或饲料的蒸汽灭菌——所谓的蒸煮工艺。
本发明因此优选涉及根据本发明的用途,其中该用途适于在高温下的处理,特别是加热或烹饪该包装中的食品、所谓的袋内泡煮、所谓的食品或饲料的热填充、所谓的热填充、或填充到多层复合物中之后食品或饲料的蒸汽灭菌——所谓的蒸煮工艺。
本发明进一步涉及包括根据本发明的多层复合物的包装。
实施例
原材料/所用材料:
聚酯膜:RNK23μm未处理的Mitsubishi Polyester Film,D-65203Wiesbaden
铝箔:纯铝箔合金8011 12μm,KorffAG,CH-4538 Oberbipp,瑞士
PVC印刷墨:粘结剂:聚氯乙烯,颜色:白色;溶剂:乙酸乙酯
PU印刷墨:粘结剂:聚氨酯;颜色:白色;溶剂:乙酸乙酯
制造所用聚氨酯分散体:
PUD 1:
800.2克由己二酸、间苯二甲酸和1,6-己二醇制备的OH值为56的聚酯二醇和26.74克二羟甲基丙酸在90℃和50mbar(绝对压力)下脱水60分钟。混合物随后初始在持续搅拌下在80℃下均化15分钟,随后加入197.4克异佛尔酮二异氰酸酯(IPDI),将混合物加热到110℃并将该温度保持恒定在110℃。在1小时15分钟后,达到2.35重量%的恒定异氰酸酯含量。为了溶解形成的预聚物,加入1540克丙酮,混合物在48℃下搅拌20分钟。随后在搅拌下在48℃下用溶解在50克丙酮中的15.13克三乙胺中和。15分钟后,在48℃加入10.35克乙二胺、2.40克二乙醇胺和115克水的混合物并再搅拌30分钟。随后在剧烈搅拌下向丙酮预聚物混合物添加1460克水并在48℃下分散20分钟。蒸馏去除丙酮获得固含量为40.0重量%的水性分散体。
PUD 2:
909.4克由己二酸、间苯二甲酸和1,6-己二醇制备的OH值为56的聚酯二醇和30.4克二羟甲基丙酸在90℃和50mbar(绝对压力)下脱水60分钟。混合物随后初始在持续搅拌下在80℃下均化15分钟,随后加入224.4克异佛尔酮二异氰酸酯(IPDI),将混合物加热到110℃并将该温度保持恒定在110℃。在1小时20分钟后,达到2.29重量%的恒定异氰酸酯含量。为了溶解形成的预聚物,加入1750克丙酮,混合物在48℃下搅拌20分钟。随后在48℃加入在140克水中的15.64克乙二胺的溶液并搅拌30分钟。随后,在搅拌下,在48℃下经5分钟滴加18.12克25重量%的氨水溶液并再搅拌15分钟。随后在剧烈搅拌下向丙酮预聚物混合物添加1640克水并在48℃下分散20分钟。蒸馏去除丙酮获得固含量为40.2重量%的水性分散体。
PUD 3:
909.4克由己二酸、间苯二甲酸和1,6-己二醇制得的OH值为56的聚酯二醇和30.4克二羟甲基丙酸在90℃和50mbar(绝对压力)下脱水60分钟。混合物随后初始在持续搅拌下在80℃下均化15分钟,随后加入224.4克异佛尔酮二异氰酸酯(IPDI),将混合物加热到110℃并将该温度保持恒定在110℃。在1小时20分钟后,达到2.37重量%的恒定异氰酸酯含量。为了溶解形成的预聚物,加入1750克丙酮,混合物在48℃下搅拌20分钟。随后在48℃加入在160克水中的17.82克乙二胺的溶液并搅拌30分钟。随后,在搅拌下,在48℃下经5分钟滴加16.81克25重量%的氨水溶液,并再搅拌15分钟。随后在剧烈搅拌下向丙酮预聚物混合物添加1625克水并在48℃下分散20分钟。蒸馏去除丙酮获得固含量为40.1重量%的水性分散体。
PUD 4:
800.2克由己二酸、间苯二甲酸和1,6-己二醇制备的OH值为56的聚酯二醇和26.74克二羟甲基丙酸在90℃和50mbar(绝对压力)下脱水60分钟。混合物随后初始在持续搅拌下在80℃下均化15分钟,随后加入196.38克异佛尔酮二异氰酸酯(IPDI)与1.74克Desmodur N3300(六亚甲基二异氰酸酯的三聚体;Covestro AG Deutschland)的混合物,将混合物加热到110℃并将该温度保持恒定在110℃。在1小时后,达到2.35重量%的恒定异氰酸酯含量。为了溶解形成的预聚物,加入1540克丙酮,混合物在48℃下搅拌20分钟。随后在48℃加入在124克水中的13.76克乙二胺的溶液并搅拌30分钟。随后,在搅拌下,在48℃下经5分钟滴加18.45克25重量%的氨水溶液,并再搅拌15分钟。随后在剧烈搅拌下向丙酮预聚物混合物添加1450克水并在48℃下分散20分钟。蒸馏去除丙酮获得固含量为40.1重量%的水性分散体。
交联剂:
Desmodur XP 2802:大约40重量%的多碳二亚胺水性分散体,碳二亚胺含量为大约1DCC eq.(mmol/g),Covestro Deutschland AG
粘合剂分散体:
实施例1:100重量份PUD 1+13.5重量份Desmodur XP 2802
实施例2:100重量份PUD 2+13.5重量份Desmodur XP 2802
实施例3:100重量份PUD 3+13.5重量份Desmodur XP 2802
实施例4:100重量份PUD 4+13.5重量份Desmodur XP 2802
制造膜复合物:
Labo Combi 400:实验室用双层压机,来自意大利Nordmeccanica公司。该层压机具有用于低能膜表面预处理的在线电晕工位和用于蒸发溶剂与水的隧道式干燥器。
印刷聚酯膜
使用Labo Combi 400将印刷墨施加到聚酯膜上。在印刷前对该聚酯膜施在线以电晕预处理。聚酯膜的表面能在所有情况下均>40mN/m。
用乙酸乙酯将印刷墨调节至加工粘度。使用凹印辊在凹版印刷工艺中进行印刷墨的施加。带速度在每种情况下为30m/min。涂有印刷墨的膜带随后穿过隧道式干燥器。隧道式干燥器中的温度为70℃。将整体印刷层在溶剂闪蒸后的涂施重量在每种情况下调节至2g/m2。
制造由PET/印刷墨/胶粘剂/铝箔组成的多层复合物
用Labo Combi 400设备制造该多层复合物。使用凹印辊将根据实施例1至4的各自具有大约40重量%的聚合物比例的水性胶粘剂分散体施加到聚酯膜的印刷侧上。由此获得的胶粘剂层在70℃下在隧道式干燥器中干燥。随后在加热至40℃的层压机中在压力下将铝箔与涂有胶粘剂的印刷聚酯膜层压。
表1:粘合剂涂施重量
实施例 | 无印刷墨 | PVC印刷墨 | PU印刷墨 |
1 | 4.6 | 5.1 | 5.7 |
2 | 4.4 | 5.0 | 4.5 |
3 | - | - | 4.0 |
4 | - | - | 5.6 |
所有数据以g/m2计
获得以下结构的复合物:
V1(对比)PET/来自实施例1至4的胶粘剂/铝箔
V2(对比)PET/完全用PVC印刷墨印刷(涂施重量2.0g/m2)/来自实施例1至4的胶粘剂/铝箔
3(发明)PET/完全用PU印刷墨印刷(涂施重量2.0g/m2)/来自实施例1至4的胶粘剂/铝箔
储存和分层试验:
在储存的样品(膜层压体)上的拉伸剪切测试:为此,样品储存在23℃/50%相对湿度下。1周后测定复合物强度。此外,在1周后,在120℃下60分钟和134℃下60分钟的条件下灭菌后,将储存的复合物再储存24小时,然后测试拉伸剪切强度。
需要/应当讨论灭菌吗?
对获得的复合物V1、V2或3进行储存和分层试验。结果显示在表2中:
表2:储存和分层试验的结果
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DEL 分层
f 实验过程中撕裂
F 试样已经在粘合接缝中/处撕裂(在夹紧前)
多层复合物V2(使用PVC印刷墨)在对应于蒸汽灭菌器中的处理的条件(即121℃下60分钟或134℃下60分钟)下分层。
多层复合物3(使用PU印刷墨)即使在对应于蒸汽灭菌器中的处理的条件(即121℃下60分钟或134℃下60分钟)下也始终达到高值。
Claims (11)
1.多层复合物,其至少包括第一聚合物层和第二层,所述第一聚合物层在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨,所述第二层使用聚氨酯分散体作为粘合剂至少部分粘结到所述第一聚合物层涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的所述侧上。
2.根据权利要求1所述的多层复合物,其特征在于所述至少一个第一聚合物层的材料选自聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)、聚酯、聚乙酸酯、赛璐酚、聚乳酸(PLA)及其混合物。
3.根据权利要求1或2所述的多层复合物,其特征在于所述至少一个其它层是聚合物层或由至少一种金属、优选铝组成的层。
4.根据权利要求1至3任一项所述的多层复合物,其特征在于作为粘合剂使用至少一种1K聚氨酯分散体。
5.根据权利要求1至4任一项所述的多层复合物,其特征在于作为粘合剂使用至少一种聚氨酯分散体,其是至少一种水性聚氨酯分散体(I)和至少一种亲水化多碳二亚胺的至少一种水性分散体(II)的混合物。
6.根据权利要求1至5任一项所述的多层复合物,其特征在于所述第一聚合物层由聚酯组成,且所述第二层由铝组成。
7.用于制造根据权利要求1至6任一项所述的多层复合物的方法,至少包括以下步骤:
(A)提供至少一个在至少一侧上涂有至少一种含有至少一种聚氨酯作为粘结剂的印刷墨的第一聚合物层,
(B)将作为粘合剂的聚氨酯分散体施加到第一聚合物层上,
(C)使来自步骤(B)的第一聚合物层与至少一个第二层接触以获得根据本发明的多层复合物。
8.根据权利要求7所述的方法,其特征在于步骤(B)中作为粘合剂使用至少一种允许单组分加工的聚氨酯分散体。
9.根据权利要求1至6任一项所述的多层复合物用于包装食品或饲料的用途。
10.根据权利要求9所述的用途,用于在高温下的处理,特别是加热或烹饪所述包装中的食品或饲料、所谓的袋内泡煮、所谓的食品或饲料的热填充、所谓的热填充、或填充到多层复合物中之后食品或饲料的蒸汽灭菌——所谓的蒸煮工艺。
11.包括根据权利要求1至6任一项所述的多层复合物的包装。
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EP21158330.7A EP4046794A1 (de) | 2021-02-22 | 2021-02-22 | Mehrschichtverbunde aus bedruckten folien |
PCT/EP2022/054030 WO2022175424A1 (de) | 2021-02-22 | 2022-02-18 | Mehrschichtverbunde aus bedruckten folien |
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EP (2) | EP4046794A1 (zh) |
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DE3603996A1 (de) | 1986-02-08 | 1987-08-13 | Bayer Ag | Verfahren zur kontinuierlichen herstellung von waessrigen polyurethandispersionen und ihre verwendung als beschichtungsmittel oder als klebstoff |
CA2239718C (en) | 1998-06-04 | 2004-08-17 | H.B. Fuller Licensing & Financing, Inc. | Aqueous laminating adhesive composition, and dry bonded laminate comprising flexible film substrates bonded by two blended parts at time of use |
ES2198375T5 (es) | 2001-02-05 | 2009-11-23 | Siegwerk Benelux Nv | Resina de poliuretano, composicion de revestimiento que comprende una resina de poliuretano, uso de una resina de poliuretano para imprimir sustratos de plastico, un metodo para producir una resina de poliuretano, metodo para producir estratificado que tiene una imagen impresa. |
ATE304564T1 (de) | 2003-07-11 | 2005-09-15 | Sicpa Holding Sa | Polyurethanharz für farbtinten |
EP1496072B1 (en) | 2003-07-11 | 2005-11-02 | Sicpa Holding S.A. | A polyurethane resin for white inks |
DE202004019009U1 (de) * | 2004-12-07 | 2005-03-31 | Wipak Walsrode Gmbh & Co Kg | Metallisierte Mehrschichtfolie |
KR20140101841A (ko) | 2011-12-09 | 2014-08-20 | 바스프 에스이 | 수성 폴리우레탄 분산액의 복합 필름 라미네이션용 용도 |
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DE102017204525A1 (de) * | 2016-03-23 | 2017-09-28 | Basf Se | Verbundfolienlaminate für flexible Verpackungen |
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WO2022175424A1 (de) | 2022-08-25 |
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